Treatment of a waste stream through production and utilization of oxyhydrogen gas

ABSTRACT

Methods and systems for reducing a redox active contaminant in a waste stream in a waste treatment system involve performing a unit process of the waste treatment system by contacting redox active contaminant in the waste stream with oxyhydrogen-rich gas generated on-site by an oxyhydrogen gas generator that implements water dissociation technology. The oxyhydrogen gas generator involves applying a pulsed electrical signal to a series of closely spaced electrodes that are submerged in the waste stream to produce oxyhydrogen-rich gas from a water component of the waste stream. Operation of the oxyhydrogen gas generator in the waste stream may accomplish one or more unit processes for waste treatment, such as oxidation, stripping, floatation, disinfection, conditioning, stabilization, thickening, and dewatering, among others.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 11/565,240 filed Nov. 30, 2006, which is a continuation-in-partof U.S. patent application Ser. No. 10/717,951 filed Nov. 19, 2003, nowU.S. Pat. No. 7,160,472, which claims the benefit of priority of U.S.provisional patent application Ser. No. 60/427,921 filed Nov. 19, 2002.All of the above applications are hereby incorporated herein byreference in their entirety.

FIELD

This application relates to methods and systems for treating wastestreams, such as industrial waste water, municipal waste water andothers.

BACKGROUND

Harmful materials found in many waste streams can present a significantrisk to the environment and/or human health if left untreated.Government regulations often mandate that various organic, inorganic,chemical, and microbial components of a waste stream must be treatedbefore the waste stream can be discharged to the environment. Examplesof such waste streams include industrial and municipal wastewater,chemical processing effluent, animal waste, paper mill effluent, andothers.

FIG. 1 presents a schematic of a treatment facility illustrative ofprior art systems for treating municipal wastewater. With reference toFIG. 1, wastewater influent 100 enters a primary clarifier 102 of thewastewater treatment facility where raw sludge 104 is separated from thewastewater via flocculation, sedimentation, and other primary settlingtechniques. The wastewater from the primary clarifier 102 is thentransported to an aeration basin 106, in which aerobic microorganisms108 help treat the wastewater in the presence of air 110 that is pumpedinto the aeration basin 106. The wastewater is then transferred to asecondary clarifier 112, in which further settling can occur. Secondarysludge 114 is also collected in the secondary clarifier, and the treatedwastewater 116 is transported to an effluent body of water or otherdistribution source (sometimes only after being subjected to certainadvanced treatment procedures such as disinfection, for example).

Some of the secondary sludge 114 is recycled 118 back into the aerationbasin 106 to help perpetuate the aerobic biodegradation process. Theremaining secondary sludge 114 from the secondary clarifier 112 and theraw sludge 104 from the primary clarifier 102 are transported via adigester feed 120 to an anaerobic digester 122. In the anaerobicdigester 122, anaerobic microorganisms 124 further degrade the sludgeand yield by-product gases 126, such as methane 128. The digested sludgefrom the anaerobic digester 122 is transferred off as liquid 130 whichcan be applied directly to agricultural land or can be sent to adewatering process 132. From the dewatering process, the centrate orliquid fraction 134 is typically returned to the front end of thetreatment plant 100 for treatment, and the dewatered sludge cake 136 canbe used for incineration, land application, or other appropriate uses.

Biosolids are a mixture of water and very small solid particles(primarily bacteria and protozoa). The particles carry a net negativecharge that resists flocculation, i.e., the agglomeration of smallerparticles into larger composite particles. In order to produce a matrixthat has sufficient porosity to allow the movement of water through thematrix and accomplish dewatering, an organic polyelectrolyte or polymeris typically added to biosolids as a conditioning aid. In simple terms,these polymers are essentially long organic strands or ribbons with manyactive sites that have a net positive charge. The polymer neutralizesthe negative charge on the biosolids and binds a particle to each activesite on the polymer. The polymers have a tendency to stick to each otherwith the net effect that larger particles are created and the result isa porous matrix through which water can drain during the dewateringprocess.

Traditional polymer conditioning has a number of problems associatedwith it. Polymers are expensive and can account for a significantportion of the operating cost of a biosolids processing budget. Thecharacteristics of biosolids change on a continual basis and it isdifficult to provide the exact amount of polymer required at any giventime to ensure that adequate performance is achieved without overdosingand wasting the polymer. The polymers normally used for conditioningbiosolids are high molecular weight, high charge density materials,which are resistant to biological degradation and are known to be toxicto aquatic organisms. There is concern that any overdose of polymercould result in a release of the excess into the environment with toxiceffects on fish and other aquatic species. The breakdown of polymers instored biosolids has also been associated with the production ofsignificant odors.

Waste streams may also be treated by incineration. Incineration is oneof the few technologies that offers a technically sound solution for thecomplete destruction of pathogens, viruses, and toxic organics. Inaddition, it has the capability to process biosolids that contain highlevels of contaminants, and which are, therefore, unacceptable foragricultural utilization. However, the high capital cost of aconventional incinerator and the extensive pre-processing (e.g.,dewatering) of the biosolids make the process very expensive. Thus,incineration has typically been economical only in very large wastewatertreatment facilities, in which it is possible to benefit from economy ofscale.

In order to avoid the consumption of prohibitively expensive quantitiesof imported energy during the combustion process of prior artincineration systems, the biosolids must be dewatered to a cake withapproximately 30% solids. At this level of dryness, the cake is aplastic, sticky, semi-solid material that can present significantoperational problems related to the transfer of the cake from thedewatering device to the incinerator. Variations in the solids contentof the cake and attendant variations in heat demand can also make thecombustion process very difficult to control.

Stabilization of biosolids is a mandatory prerequisite for agriculturalutilization of waste sludge and, depending upon the specific location,may be regulated by federal, state, or provincial authorities. Theregulations protect human health and the environment from potentialrisks associated with pathogens contained in the biosolids. Regulatorybodies typically stipulate which treatment processes are acceptableand/or what levels of specific pathogens are allowable in the treatedproduct. Conventionally, stabilization occurs through one or more of thefollowing processes: biological degradation of organic matter, elevatedpH, reduction of moisture, and waste handling according to specifictime/temperature regimes. All of these processes are relativelyexpensive, and may be energy intensive, require large volumes ofadmixtures, or be difficult to control.

The electricity needed to operate conventional wastewater treatmentfacilities has traditionally been purchased from a distribution grid.There has been little incentive to generate electricity on site becausepower from the grid has been cheap and secure, the capital cost forgenerating equipment is high, and the only cheap source of fuel forpower production is digester gas. However, there are a number ofproblems with utilizing digester gas as an energy source. Although itcontains a high percentage of methane, digester gas is also saturatedwith water and contains significant quantities of hydrogen sulfide. Thismakes digester gas extremely corrosive, and extensive cleaning isrequired prior to its use. Furthermore, digester gas is only thebyproduct of a waste treatment process, as opposed to being a productionprocess in itself. The amount of gas produced is a function of thebiosolids stabilization process and cannot be modified to meet changingdemands. The combustion of methane-rich biogas also generatessignificant greenhouse gas emissions.

After most solids have been separated from influent wastewater, theremaining effluent is typically disinfected in preparation for itsrelease into the environment. The disinfection of wastewater effluenthas been historically accomplished through the addition of chlorinecompounds. There are major health and safety concerns associated withhandling chlorine compounds. In recent years, there have been increasedconcerns that chlorine can combine with organic material in the effluentto produce chlorinated organics, which are both toxic and potentiallycarcinogenic. Although some efforts are being made to substitute lesstoxic chlorine compounds, there is an industry-wide trend towardsphasing out the use of chlorine as a disinfectant agent.

Other disinfection technologies employed in wastewater treatment involvethe use of ultra-violet (UV) light or ozone to destroy the pathogens.Neither of these processes leaves any appreciable residual in thetreated effluent to impact on the environment. However, the capital andoperating costs of both of these systems are relatively high. In thecase of a UV process, the capital costs include the construction of theflow-through mechanism, and the multiple UV bulbs (lamps) that arerequired. The operating costs include power, the replacement of bulbs,and regular cleaning of the bulbs. The major costs for disinfecting withozone include the ozone generator and the commercial oxygen, which isused as the feed source. When air is used as the feed source, the sizeof the ozone generator must be approximately doubled, therefore doublingthe capital cost.

More recently, additional attention has been placed on the presence oforganic, inorganic and chemical components such as pharmaceuticalproducts, petrochemical products, personal care products and metals.Personal care products can include, for example, prescription andover-the-counter therapeutic drugs, veterinary drugs, fragrances andcosmetics. The removal of these components from a waste stream hasbecome more and more important.

Many of the uses for water in a waste treatment facility requirerelatively high quality water that is free of suspended particulatematter, but there is no need for it to be chlorinated or to have achlorine residual present, as is the case for potable water. Finaleffluent does not meet these criteria due to the presence of suspendedsolids. It is therefore unsuitable as an alternative for applicationssuch as making up polymer, because the suspended solids generate apolymer demand in the makeup water itself Currently, waste treatmentplants have no alternative for these higher quality end uses other thanthe use of potable water, which they must purchase from the municipalwater supply system.

There is thus a need for improved methods and systems for flocculation,incineration, dewatering, energy efficiency, stabilization, effluentdisinfection, chemical removal and production of high quality processwater in a wastewater treatment plant and for treating other kinds ofwaste streams. The methods and systems provided herein are intended toalso remove pharmaceuticals, personal care products and petrochemicalproducts from the waste water.

SUMMARY

Methods and systems for reducing a redox active contaminant in a wastestream in a waste treatment system involve performing a unit process ofthe waste treatment system by contacting the redox active contaminant inthe waste stream with oxyhydrogen-rich gas generated by an oxyhydrogengas generator that implements water dissociation technology. In oneembodiment, the oxyhydrogen gas generator applies a pulsed electricalsignal to a series of closely-spaced electrodes that are submerged inthe waste stream to produce oxyhydrogen-rich gas from a water componentof the waste stream. Operation of the oxyhydrogen gas generator in thewaste stream may accomplish one or more unit processes for wastetreatment, such as conditioning, stabilization, thickening, anddewatering, among others.

At least a portion of the oxyhydrogen-rich gas can be conveyed for asecond use in the waste treatment system, such as a source ofcombustible fuel for incineration or power generation, for example.Oxygen may also be separated from the oxyhydrogen-rich gas for use inaeration basin of the waste treatment system or to supply an ozonegenerator that may be utilized in the disinfection of effluent of thewaste treatment system. Exhaust from the combustion of theoxyhydrogen-rich gas can be condensed to recover water for various useswithin the treatment system.

According to one aspect herein, there is provided a method for removinga redox active contaminant from a waste stream, comprising: submersingtwo closely spaced electrodes in the waste stream, the waste streamcomprising a water component and the redox active contaminant, theelectrodes bordering an interaction zone extending therebetween;applying a pulsed electrical signal to at least one of the electrodesthereby generating oxyhydrogen-rich gas from the water component, theoxyhydrogen-rich gas forming bubbles in the interaction zone that riseto a surface of the waste stream, wherein at least some of the bubblescontact the redox active contaminant as they rise through the wastestream thereby transporting at least a portion of the redox activecontaminant to the surface of the waste stream.

In a particular case, the two closely spaced electrodes may be steelelectrodes and the method may further include: submersing two closelyspaced aluminum electrodes in the waste stream downstream of the steelelectrodes, the aluminum electrodes bordering a second interaction zoneextending therebetween; and applying a pulsed electrical signal to atleast one of the aluminum electrodes thereby generating oxyhydrogen-richgas from the water component, the oxyhydrogen-rich gas forming bubblesin the second interaction zone that rise to a surface of the wastestream.

According to another aspect herein, there is provided a system forremoving a redox active contaminant from a waste stream, the wastestream including a water component, the system comprising: two closelyspaced electrodes to be submersed in the waste stream, the electrodesdefining an interaction zone extending therebetween; a power supply forapplying a pulsed electrical signal to at least one of the electrodes togenerate from the water component oxyhydrogen-rich gas which will formbubbles in the interaction zone that rise to a surface of the wastestream; a reaction vessel to contain the bubbles as they rise; a gascontainment lid to trap above the waste stream a mixture of theoxyhydrogen-rich gas and the redox active contaminant of the wastestream, the mixture formed by those of the bubbles that contact aportion of the redox active contaminant that transport the portion tothe surface of the waste stream; and transport system for transportingthe mixture to further treatment.

In a particular case, the two closely spaced electrodes may be steelelectrodes and the system may further include: two closely spacedaluminum electrodes to be submersed in the waste stream downstream ofthe steel electrodes, the electrodes defining a second interaction zoneextending therebetween, and wherein the power supply applies a pulsedelectrical signal to at least one of the aluminum electrodes to generatefrom the water component oxyhydrogen-rich gas which will form bubbles inthe second interaction zone that rise to a surface of the waste stream.It will be understood that the aluminum electrodes may be in a separatearea from the steel electrodes and that the residence time for each setof electrodes may be different and may depend on various factors relatedto the waste stream. Further, the pulsed electrical signal may beprovided by a single or multiple sources and may be the same ordifferent for each set of electrodes.

In the above cases, the redox active contaminant may be a pharmaceuticalor, more generally, a personal care product. The pharmaceutical may bebenzafibrate, carbamazepine, fluozetine, sulfamethoxazole, trimethoprim,ibuprofen, naproxen or diclofenac. In another particular case, the redoxactive contaminant may be caffeine or the like.

Additional aspects and advantages will be apparent from the followingdetailed description of embodiments, which proceeds with reference tothe accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram illustrating components of a wastewatertreatment facility in accordance with the prior art.

FIG. 2 is a schematic diagram illustrating treatment of a waste streamvia a waste treatment system in accordance with an embodiment herein.

FIG. 3 is a schematic diagram illustrating a waste treatment system inaccordance with embodiments in which oxyhydrogen gas generationapparatuses may be used to perform one or more unit processes in a wastetreatment system.

FIG. 3A is a schematic diagram illustrating a wastewater treatmentfacility in which an oxyhydrogen gas generation apparatus isincorporated between an anaerobic digester of the facility and adewatering process for performing conditioning and/or flocculation unitprocesses.

FIG. 3B is a schematic diagram illustrating a wastewater treatmentfacility utilizing an oxyhydrogen gas generation apparatus in lieu of ananaerobic digester for performing a stabilization unit process.

FIG. 3C is a schematic diagram illustrating a wastewater treatmentfacility utilizing an oxyhydrogen gas generation apparatus fordewatering preliminary to an incineration unit process.

FIG. 4 is a schematic diagram illustrating typical secondary uses foroxyhydrogen-rich gas produced by one or more unit processes employing anoxyhydrogen gas generation apparatus according to FIGS. 2, 3A, 3B, 3C,and 5.

FIG. 5 is a schematic diagram illustrating an apparatus consistent withthe various embodiments and displaying its application in the treatmentof wastewater biosolids in a wastewater treatment facility, as in theembodiments of FIGS. 3A, 3B, and 3C, for example.

DETAILED DESCRIPTION

Throughout the specification, reference to “one embodiment”, “anembodiment,” or “some embodiments” means that a particular describedfeature, structure, or characteristic is included in at least oneembodiment. Thus appearances of the phrases “in one embodiment,” “in anembodiment,” or “in some embodiments” in various places throughout thisspecification are not necessarily all referring to the same embodiment.

Furthermore, the described features, structures, characteristics, andmethods may be combined in any suitable manner in one or moreembodiments. Those skilled in the art will recognize that the variousembodiments can be practiced without one or more of the specific detailsor with other methods, components, materials, etc. In other instances,well-known structures, materials, or operations are not shown or notdescribed in detail to avoid obscuring aspects of the embodiments.

As noted above, there is an increased interest in the removal ofchemical components such as pharmaceutical products, petrochemicalproducts, personal care products and metals from waste water streams.While previously unanticipated, it has now been demonstrated that thereare additional benefits to the treatment of an influent waste streamwith oxyhydrogen-rich gas. In addition to the reduction of ammonia,phosphorous, suspended solids, pathogens and organic material (measuredas Biochemical Oxygen Demand, or BOD) in the waste stream, it has nowbeen shown that treatment of a waste stream with oxyhydrogen-rich gascan also reduce the concentration of redox-active organic contaminants(such as pharmaceutical, personal care products and petrochemicalproducts). In addition, refinements of the process of treatment withoxyhydrogen-rich gas have shown an improved reduction or removal ofredox-active organic contaminants.

FIG. 2 is a schematic diagram illustrating treatment of a waste stream202 via a simplified waste treatment system 204 in accordance with afirst embodiment. With reference to FIG. 2, waste stream 202 maycomprise an influent waste stream, such as industrial or municipalwastewater (raw sewage which may include pharmaceutical, personal careproducts and petrochemical products), for example. Alternatively, wastestream 202 may comprise an intermediate waste stream such as supernatantor biosolids, for example, in the context of a larger waste treatmentprocess. In still other embodiments, waste stream 202 may includechemical processing effluent, animal waste, paper mill effluent,landfill leachate, marine wastewater, storm water runoff, ground water,surface water, in-situ treatment process effluent, and environmentalcontaminate remediation process effluent, for example. Waste stream 202may be subjected to preliminary processing steps, such as screening andgrit removal, before undergoing a unit process 206, as described below.Screening and grit removal may be particularly important when wastestream 202 comprises raw sewage influent.

In one embodiment, unit process 206 comprises an oxyhydrogen gasgenerator 207 (001) interposed in a flow path 208 between an inlet 210and an outlet 212 of waste treatment system 204 for generatingoxyhydrogen-rich gas 214 from a water component of waste stream 202.Oxyhydrogen-rich gas 214 generated from waste stream 202 preferablybubbles through or otherwise passes through at least a section of flowpath 208 to thereby contact at least a portion of waste stream 202. Insome embodiments, the water component is segregated from the wastestream 207 through use of a semipermeable membrane or other separationtechnology and the gas generator 207 is immersed in the segregated watercomponent. In other embodiments, oxyhydrogen-rich gas may be generatedexternal to flow path 208 and added at unit process 206 to contact atleast a portion of waste stream 202. For example, a source of water forthe oxyhydrogen gas generator 207 may include tap water, surface water,or a water component that has been separated from the waste stream.

Unit process 206 may operate as a one-step wastewater treatment process,in which the concentrations of contaminants, examples of which are:Biochemical Oxygen Demand (BOD), ammonia, phosphorous, suspended solidsand pathogens are reduced in waste stream 202. Unit process 206 mayadditionally operate as a wastewater treatment process in which theconcentration of organic, inorganic and chemical contaminants, such aspharmaceutical, personal care products, petrochemical products, andmetals, are reduced in waste stream 202. The contaminants to be removedfrom waste stream 202 using the produced oxyhydrogen-rich gas 214 aregenerally considered as: (a) contaminants which can be oxidized thoughcontact with the oxidants contained in the oxyhydrogen-rich gas 214(i.e. they are “oxidizable contaminants”), and (b) contaminants whichcan be reduced through contact with the hydrogen contained in theoxyhydrogen-rich gas 214 (i.e. they are “reducible contaminants”). Thatis to say, the contaminants to be removed from waste stream 202 usingthe produced oxyhydrogen-rich gas 214 can be called reduction-oxidation(“redox”) active (“redox active contaminants”) under the conditions ofthe process 206. Contaminants are removed from waste stream 202 viaoperation of the gas generation apparatus in flow path 208. For example,where waste stream 202 comprises municipal wastewater, organiccontaminants, such as pharmaceutical, personal care products andpetrochemical products, are believed to be oxidized by the oxidizingcompounds contained in the oxyhydrogen-rich gas 214.

Volatile contaminants, which evaporate to varying degrees at normalwastewater processing temperatures, such as ammonia (inorganic) andacetone, toluene, dichloromethane and dichlorobenzene (organic) arestripped (transferred from the liquid phase to the gas phase) from thewastewater through the upward flow of oxyhydrogen-rich gas 214 producedby oxyhydrogen gas generator 207 (GG1). Solid-phase contaminants such assuspended solids and phosphorous are removed through the naturalflotation mechanism created by oxyhydrogen-rich gas 214 which isproduced in the form of micro-bubbles from the oxyhydrogen gas generator207 (GG1). The stripped volatile contaminants are collected at thesurface of the unit process 206 in combination with the oxyhydrogen-richgas 214 and are conveyed to a secondary process module 222 where theymay be combusted with the oxyhydrogen-rich gas 220 or separated from theoxyhydrogen-rich gas by processes such as membranes for furthertreatment (not shown). The solid fraction 216 can be removed from theliquid stream either directly, by skimming the float layer from unitprocess 206 or by subsequent sedimentation. In this embodiment as aone-step wastewater treatment process, biological processes are notintended as a component of unit process 206 and therefore the productionof biosolids is not intended to occur. The solid fraction in thisembodiment is not intended to be biosolids but rather consists of inert,inorganic solids 216 that can be directly disposed of in landfillwithout further treatment. The treated waste stream is concurrentlydisinfected of pathogens so that it meets regulatory and industrystandards for effluent 218. Thereafter effluent 218 may be releaseddirectly to a body of surface water such as a river, for example, orreused in waste treatment system 204. In alternative embodiments,effluent 218 may undergo further processing (not shown) such as tertiarysand filtration after unit process 206 and before release or reuse.

After contacting waste stream 202, exiting amounts of oxyhydrogen-richgas 220 may be conveyed from unit process 206 to a secondary processmodule 222 of waste treatment system 204, such as an incineration unit,for example. FIG. 4, described below, illustrates various othersecondary uses for oxyhydrogen-rich gas 220 following its utilization inunit process 206. Depending on the kind of secondary use for whichoxyhydrogen-rich gas 220 is employed, unused oxyhydrogen-rich gas or aby-product 224 of secondary process 222, may be recovered or otherwiseconveyed to one or more other process modules 226 for use in tertiaryaspect(s) of waste treatment system 204 or external use(s).

Oxyhydrogen gas generator 207 may implement a water dissociationtechnology, such as the kind disclosed in U.S. Pat. Nos. 6,419,815 and6,126,794 of Chambers, both issued to Xogen Technologies Inc. andincorporated herein by reference (hereinafter “the Xogen patents”). Asdescribed in the Xogen patents at columns 3-5, gas generationapparatuses in accordance with embodiments include electrode “cells”each including two or more spaced-apart electrodes adapted to beimmersed in a working fluid including water. In the embodimentsdescribed herein, the working fluid comprises waste stream 202. Theelectrodes are preferably made of the same material. One electrodematerial is stainless steel for its low cost and durability, but it maybe possible to use other conductive metals. An equal spacing between theelectrodes is maintained and it is preferable to minimize the spacingbetween the electrodes. However, the spacing between the electrodescannot be positioned excessively close because arcing between theelectrodes would occur. It has been determined that a spacing of 1 mm orless is optimal spacing for producing oxyhydrogen-rich gas, but anincreased spacing of up to approximately 5 mm may work effectively whilebeing less subject to fouling due to accumulation of solids between theelectrodes. A spacing above 5 mm may also be feasible, but tends toreduce the output of oxyhydrogen gas and increases power requirements.

It is preferable to include many pairs of electrodes (e.g. dozens orhundreds) within each cell. The electrodes can be almost any shape, butpreferably comprise flat plates closely spaced and parallel to eachother. Alternative embodiments may include coaxially aligned cylinders.Insulating spacers can be interposed between adjacent electrodes tomaintain equal spacing between the electrodes and to prevent currentleakage therebetween.

As further described in the Xogen patents, a high-frequency pulseddirect current (DC) electrical signal is applied to the electrodes. Thepulsed signal can be almost any waveform and have a variable currentlevel, voltage level, frequency and mark-space ratio (i.e., a ratio ofthe duration of a single pulse to the interval between two successivepulses). The source of power for the power supply may include a mains110 volts or batteries, such as 12-volt car batteries. For example, thepower supply may comprise two 12-volt batteries arranged in series toprovide a 24-volt supply. For powering a large-scale gas generator GG1in a large waste treatment system such as a municipal wastewatertreatment plant, a more complex power supply may be required forgenerating 24-volt pulsed DC signal having sufficient power to drive thelarge cells required. Alternatively, multiple smaller electrode cellsmay be provided for redundancy and spaced apart in a reaction vessel orother reaction zone, in which case the cells may be driven by simplerindependent power supplies.

A controller is used in conjunction with the batteries or other powersource to generate one of a variety of pulsed output waveforms, such asa square wave, a saw tooth wave, or a triangular wave, which can beapplied to the electrodes. At present, the best results for producingoxyhydrogen-rich gas have been obtained using a square wave. In oneembodiment a pulsed signal has a mark-space ratio of betweenapproximately 1:1 and 10:1 and a pulse frequency of approximately 10Hz-250 kHz.

After initiation of the pulsed signal from the power supply, theelectrodes continuously and almost instantaneously generate bubbles ofoxyhydrogen-rich gas from water molecules in an interaction zone thatextends between the electrodes and slightly beyond the edges of theelectrodes. The generated bubbles are not bunched around or on theelectrodes and thus readily float to the surface of the fluid in thereactor vessel or other reaction zone. Therefore, there is no need toadd a chemical catalyst to assist the conduction of the solution orinhibit bubbles from bunching around or on the electrodes. Thus, manydifferent kinds of waste streams can be used as the working fluid, ascan other sources of water, such as surface water and ordinary tapwater.

FIG. 3 is a schematic diagram illustrating a waste treatment system 240in which oxyhydrogen gas generators GG2, GG3, GG4, and GG5 may be usedin the performance of one or more unit processes 242 a, 242 b, 242 c,and 242 d (collectively unit processes 242) of waste treatment system240. Oxyhydrogen gas generators GG2, GG3, GG4, and GG5 may comprisedevices similar to those described herein (items 207 and 500) withreference to FIGS. 2 and 5, for example. With reference to FIG. 3, wastetreatment system 240 is embodied as a wastewater treatment plant fortreating a waste stream 244 comprising municipal wastewater (raw sewage,which may include pharmaceutical, personal care products andpetrochemical products). However, consistent with various otherembodiments, waste treatment systems may, alternatively, be arranged andconfigured to treat different types of waste streams, such as industrialwastewater, chemical processing effluent, animal waste, paper milleffluent, landfill leachate, marine wastewater, storm water runoff,ground water, surface water, in-situ treatment process effluent, andenvironmental contaminate remediation process effluent, for example.Wastewater influent may be treated by use of a primary clarifier 246,aeration basin 248 and final clarifier 250 in accordance with knownmethods, in which biosolids 252 are removed from waste stream 244 in theforms of raw sludge 254 and waste activated sludge 256.

Before treated wastewater can be released as effluent 258, it musttypically be disinfected to prevent pathogens from entering thereceiving water where they could present a health risk. As describedabove, conventional disinfection processes utilize ultra-violet (UV)radiation, chlorine, or ozone. In accordance with one embodiment, adisinfection process 260 is either replaced or supplemented by anoxyhydrogen gas generator GG2 interposed in the flow path of the treatedwaste stream, between final clarifier 250 and effluent outlet 258. Thepulsed electrical signal applied to oxyhydrogen gas generator GG2operates to generate oxyhydrogen-rich gas and, by its operation,disinfects treated wastewater. Excess oxyhydrogen-rich gas (H₂/O₂) 262can then be conveyed to a secondary use within waste treatment system240, as described below with reference to FIG. 4. Alternatively, anoxygen component of oxyhydrogen-rich gases (H₂/O₂) produced by one ormore unit processes 242 other than disinfection unit process 242 a canbe conveyed to disinfection unit 260 as a feed source for an ozonegenerator of disinfection process 260, which may result in substantialoverall cost savings for effluent disinfection. Typically, the oxygencomponent would need to be separated from the oxyhydrogen-rich gas(H₂/O₂) before use as a feed source for an ozone generator. One possibletechnology for separating the oxygen component from the oxyhydrogen-richgas is known as pressure swing adsorption (“PSA”), a version of which isavailable in gas separation equipment sold by QuestAir Technologies Inc.of Burnaby, British Columbia, Canada. Other technologies and devices mayalso be used for separating the oxygen component from theoxyhydrogen-rich gas.

In FIG. 3 and elsewhere in this specification, the notation “H₂/O₂” isused to symbolize oxyhydrogen-rich gas, without limiting to cleanoxyhydrogen gas or to a pure gaseous mixture of diatomic hydrogen (H₂)and diatomic oxygen (O₂ ). Oxyhydrogen-rich gas is typically composed ofgas mixture including predominantly hydrogen and oxygen, but may includeat least some oxygen and hydrogen in forms other than diatomic oxygen(O₂ ) and diatomic hydrogen (H₂), such as hydroxide radicals, forexample. Oxyhydrogen-rich gas may further include measurable amounts ofcomponents other than hydrogen and oxygen that may result, for example,from the operation of the oxyhydrogen gas generator in the presence ofhigh concentrations of contaminants or from reactions of the generatedoxyhydrogen gas with contaminants in the waste streams. For example,small amounts (e.g., 1% to 4% mole fraction) of carbon dioxide (CO₂) gasmay often be present in oxyhydrogen-rich gas generated from wastewateror tap water. Trace amounts of nitrogen may also be present inoxyhydrogen-rich gas, particularly when generated from wastewater, andmay indicate breakdown of the nitrogenous compounds present in thewastewater. Furthermore, oxygen and hydrogen generated in accordancewith the embodiment gas generators GG2-GG5 are typically generated in astoichiometric ratio of approximately 1:2, respectively, notwithstandingthe lack of an indication of the stoichiometric ratio or other gascomponents in the shorthand notation “H₂/O₂” used herein.

In advance of a stabilization unit process 242 c, biosolids 252 in theform of waste activated sludge 256 may undergo a thickening unit process242 b. In accordance with one embodiment, a conventional thickeningprocess 264 such as gravity belt filtering, centrifuging, or dissolvedair floatation (DAF), for example, is supplemented or replaced by anoxyhydrogen gas generator GG3. Oxyhydrogen gas generator GG3 ispreferably interposed in the flow of waste activated sludge betweenfinal clarifier 250 and a downstream biosolids treatment process such asstabilization 242 c, conditioning 242 d, dewatering 266, drying 268and/or incineration 270, for example. The operation of oxyhydrogen gasgenerator GG3 preferably causes floatation of biosolids and othersuspended solids (i.e. collection of solids at the surface of the wastestream), which results in a concentrated floating layer that can beeasily removed or separated from the waste stream for further treatment.

In one embodiment, oxyhydrogen gas generator GG3 is submerged inwastewater contained in a reaction vessel and operated for an intervalof from approximately 60 seconds to up to approximately 10 minutes, thenpower to the gas generator GG3 is shut off. It has been found that afteran interval of operation of gas generator GG3, a substantial amount ofsolids collects on the surface of the wastewater. While a modest amountof solids may collect on the surface of the wastewater during operationof gas generator GG3, a surprisingly large increase in floating solidsoccurs nearly immediately after de-energizing of gas generator GG3 andstopping of a recycle flow through the reaction vessel (see thedescription of FIG. 5, below, for details of the recycle flow providedby pump 526). De-energizing of gas generator GG3 and stopping of therecycle flow results in quiescent conditions within the reaction vessel,which allow for unhindered floatation of solids. Preliminary experimentsshowed that after operating gas generator GG3 for an interval ofapproximately 5 minutes, then de-energizing for a period ofapproximately 2 minutes, without recycle flow, the solids concentrationin a floating layer was 4.82% as compared to 0.54% in the feed material(i.e., prior to operation of gas generator GG3). This represents aremoval of 93.5% of the sludge particles from the original feedmaterial. It should be noted that this separation efficiency, which isgenerally comparable to conventional technology, was accomplishedwithout the addition of any flocculation agents such as organicpolymers. The floatation effect of the gas generator is sometimesreferred to as “extracted gas floatation.” An extracted gas floatationunit process includes one or more cycles each including the followingsteps: (1) operating the gas generator GG3 (typically by applying ahigh-frequency pulsed electrical signal) for between approximately 60seconds and approximately 10 minutes, (2) de-energizing gas generatorGG3, (3) waiting until solids collect on the surface of the fluid(typically between approximately 30 seconds and 2 minutes), and (4)removing the solids from the surface (by skimming the surface, forexample). The cycles can be repeated continually until a desired amountof solids has been removed from the wastewater.

Biosolids 252 that are to be applied to agricultural land must typicallybe stabilized 242 c prior to application to reduce the number andviability of pathogens. Stabilization is conventionally accomplishedaerobically (by oxidation) or anaerobically (by conversion of organicmaterial to methane in the absence of oxygen). Both approaches areexpensive with aerobic stabilization being energy intensive andanaerobic stabilization being capital intensive. In accordance with oneembodiment, an oxyhydrogen gas generator GG4 is utilized forstabilization of the biosolids 252 in waste stream and generation ofoxyhydrogen-rich gas (H₂/O₂) 272. Gas generator GG4 may be submerged ina reaction vessel 502 (FIG. 3B) wherein the waste stream comes intodirect contact with the oxyhydrogen-rich gas 272 produced by gasgenerator GG4. Utilization of an oxyhydrogen gas generator GG4 forstabilization may require a shorter time of residence than required in aconventional stabilization processes 274 to kill or render innocuous aneffective amount of pathogens. Consequently, gas generator GG4 can beimmersed directly in a continuous reactor for treating biosolids as theyflow through a processing zone of the reactor. The size of the gasgenerator GG4 and the residence time required in the processing zone(i.e. the length of the flow path through the continuous reactor) is afunction of the level of stabilization required to meet regulatoryrequirements. For example, if the objective is to produce a “Class A”biosolids product meeting standards set forth in United StatesEnvironmental Protection Agency (“U.S. EPA”) Regulation 503, thefinished product must typically have a density of fecal coliform in thebiosolids of less than 1000 most probable numbers (MPN) per gram totalsolids and a “vector attraction reduction” such as a 38 percentreduction in volatile solids content. Two of the approved conventionalways to achieve this are to treat the biosolids by thermophillic aerobicdigestion at a temperature of 55° C. to 60° C. for a period of 10 days(240 hours) or under an alternative time/temperature regime of 50° C.for a period of 5 days (120 hours). By contrast, experimental studiesutilizing an oxyhydrogen gas generator GG4 have shown that thestabilization and vector attraction reduction criteria can be met with aprocessing temperature of 25° C. and a batch residence time of 4 to 6hours.

Operation of oxyhydrogen gas generator GG4 is believed to create, withina reaction vessel or flow-through processing zone, an atmosphere that isconsistent with the conditions required for stabilization. Asoxyhydrogen-rich gas is liberated, the temperature of the contents ofthe reactor or processing zone increases and can be controlled toachieve necessary temperature requirements for stabilization, in view ofa known residence time of a particular system. The time/temperatureregime can be customized to meet regulatory requirements and provide thenecessary pathogen destruction. The residence time of the liquid canalso be controlled independently of the temperature, with the resultthat any combination of time and temperature can be achieved. Followingstabilization, the biosolids can either be dewatered for agriculturalutilization or utilized directly in a liquid injection program. Theoxygen liberated by the gas generator GG4 produces a highly oxidativeenvironment resulting in the oxidation of organic matter, which can, initself, satisfy stabilization requirements. The combination of these twostabilization approaches in one step offers the potential for anextremely efficient process. The combination of these conditions may besufficient to qualify as a “Process to Further Reduce Pathogens” asspecified in U.S. EPA Regulation 503 and may produce Class A bio solidsthat can be applied, in liquid form, directly to agricultural land.Treated material may generate fewer odors and attract fewer vectors,such as flies and rodents, during the subsequent handling and reuseoperations. When these advantages are coupled with the output of energystored in the form of the liberated oxyhydrogen-rich gas 272, it isexpected that the overall cost of the stabilization unit process 242 cwill be significantly lower than for conventional stabilizationprocesses.

In some embodiments, a separate conditioning step 242 d is performedafter stabilization 242 c (either conventional 274 or via gas generatorGG4) and before dewatering 266. Conventional chemical conditioning 276involves the addition of polymers or organic polyelectrolytes tofacilitate flocculation of solid particles for removal from the wastestream. Conditioning consistent with one embodiment utilizes anoxyhydrogen gas generator GG5 to supplement or replace chemicalconditioning 276. Gas generator GG5 generates a highly oxidative andelevated temperature regime that tends to destroy polysaccharide layersaround biosolids, which can present a barrier to flocculation of thebiosolids. The reduction in polysaccharide alters surface properties ofthe biosolids to thereby decrease the amount of polymer required or, insome cases, to completely eliminate the need for polymer additives.Thus, implementation of the oxyhydrogen gas generator in theconditioning unit process 242 d reduces the cost of conditioning,reduces problems of toxicity and odor generation, and concurrentlyliberates oxyhydrogen-rich gas (H₂/O₂) 278 from a water component of thebiosolids waste stream 252. The oxyhydrogen-rich gas 278 can then berecovered and conveyed for secondary uses within waste treatment system240 or elsewhere. Similarly to stabilization 242 c, the gas generatorGG5 of conditioning process 242 d may be immersed in a reaction vessel502 (FIG. 3A) or placed in a reaction zone of a conduit or other flowpath through which the waste stream flows. Moreover, the utilization ofan oxyhydrogen gas generator may allow both stabilization andconditioning to be performed concurrently in a single combinedstabilization/conditioning unit process, as discussed below withreference to FIG. 3B.

FIGS. 3A-3C represent further illustrative embodiments of wastewatertreatment facilities including oxyhydrogen gas generators 500 forprocessing waste streams including biosolids. With respect to FIGS.3A-3C, reference numerals in the 300-series correlate to 100-seriesnumerals in the corresponding FIG. 1, described above. For example, inFIGS. 3A-3C the primary clarifier is represented by reference numeral302, which corresponds to reference numeral 102 for the correspondingunit process of FIG. 1. Details in FIGS. 3A-3C numbered with 500-seriesreference numerals are described below in greater detail with referenceto FIG. 5. With respect to FIG. 3A, a gas generator 500 is illustratedin operation between the anaerobic digester 322 and the dewateringprocess 332 for performing conditioning and/or flocculation unitprocesses. In FIG. 3B, the gas generator 500 is operated in lieu of ananaerobic digester (122 from FIG. 1) for purposes of stabilization ofthe waste stream. In the embodiment of FIG. 3B, the gas generator 500may also function as a conditioning unit process or a combinedstabilization/conditioning unit process, depending on the nature of thewaste stream entering reaction vessel 502. In FIG. 3C, the gas generator500 is operated in lieu of a conventional dewatering process (132 fromFIG. 1) as part of a combined dewatering and incineration procedureconsistent with the embodiments described.

Embodiments applied to the treatment of wastewater biosolids areschematically illustrated in further detail in FIG. 5. FIG. 5 representsone embodiment of the oxyhydrogen gas generators GG2-GG5 of FIG. 2, and,more specifically, provides additional detail of the implementation ofgas generators 500 of FIGS. 3A-3C. With reference to FIG. 5, gasgenerator 500 is submerged in a reaction vessel 502 containing a fluidsuspension 504 including water and biosolids. Fluid suspension 504 maybe dilute, as in influent wastewater, or may be more concentrated, as inactivated waste sludge, raw sludge, or thickened sludge. Fluidsuspension 504 typically includes a substantial portion of biologicalflocs (biosolids) having an aggregate specific gravity of only slightlygreater than 1.0.

Gas generator 500 may be mounted on a frame 510 that is hung from a setof floats 522 so that the submergence of the gas generator 500 ismaintained at a desired level below the surface of the fluid 504.Alternatively, gas generator 500 may be mounted to a fixed lid or otherfixed support for positioning at a fixed height in reaction vessel 502.In the embodiment shown in FIG. 5, floats 522 may also serve to seal thetop of reaction vessel 502. The frame 510 is adjustable so that thesubmergence level of the gas generator 500 can be adjusted independentof the depth of fluid 504 in the reaction vessel 502.

In another embodiment, gas generator 500 is placed on a pedestal orother support so that it is positioned below the middle of the depth offluid 504 in the reaction vessel 502. Placement of gas generator 500 lowin the reaction vessel (or other reaction zone) increases the distancethat bubbles of oxyhydrogen-rich gas must rise through fluid 504, thusincreasing their residence time and probability of contacting abiosolids particle or other treatable molecule. Preferably, gasgenerator 500 is positioned at least slightly above the floor of thereaction vessel 502 to avoid buildup of sediment and sludge between theelectrodes of the gas generator 500.

Gas generator 500 includes a series of closely-spaced electrode platesthat are oriented generally vertically and arranged such that the spacesbetween adjacent plates are open to the reactor contents at both the topand bottom edges of the plates. A pulsed electrical signal from a powersource 505 is provided to the electrode plates via power transmissionwires 507. The application of the pulsed electrical signal causes watermolecules in the fluid suspension 504 to be dissociated in aninteraction zone extending between the plates and slightly beyond theopenings between the plates, to thereby form an oxyhydrogen-rich gasincluding hydrogen and oxygen. The oxyhydrogen-rich gas collects in theinteraction zone to form bubbles that rise through the fluid suspension504 between the plates and can then be collected at the surface of thefluid suspension 504 under a gas containment lid 524. Because theaggregate density (specific gravity) of biological flocs in the fluidsuspension 504 is only marginally greater than 1.0, the rising bubblesmay transport the flocs upward and into contact with the oxygen andhydrogen in the liberated gas bubbles and/or the atmosphere collectedunder the containment lid 524.

In the process of generating oxyhydrogen-rich gas, heat is generatedaround the gas generator 500 and the temperature of the fluid suspension504 in the reaction vessel 502 may increase. A portion of the contentsof the reaction vessel 502 may be withdrawn on a continual and variablebasis and recirculated through a heat exchanger 506 via afeed/recirculation pump 526 to maintain the temperature of the fluidsuspension 504 at a desired level for the specific application inquestion. In addition to providing temperature control, therecirculation loop may also provide a degree of positive mixing in thereaction vessel 502 to help keep the bio solids in suspension and thusin a position to be transported upwards toward the surface of the fluidsuspension 504 or another contact zone where the biosolids are morelikely to contact oxyhydrogen-rich gas. Sample ports 508 may be providedin the recirculation line to allow samples of the biosolids to becollected and analyzed for various parameters in order to determine thedegree of treatment that has been achieved at any point in time.

Unit process applications for gas generator 500 in the context ofmunicipal or industrial wastewater treatment may include disinfection,thickening, conditioning, dewatering, and stabilization, for example, asdescribed herein. The combination of operating parameter levels can beoptimized for each kind of unit process and may be unique for eachapplication and for each waste stream source. Some of the operatingparameters, which can be independently varied, include the submergencedepth of the gas generator 500, the magnitude of the power provided togas generator 500 via power supply 505, the characteristics of thepulsed electrical signal to the electrodes of the gas generator 500, andthe temperature and the residence time of the fluid suspension 504within the reaction vessel 502. Characteristics of the pulsed electricalsignal that may be controlled by power supply 505 include pulsefrequency, amplitude, pulse duration, mark:space ratio, waveform (i.e.,square wave, saw tooth wave, etc.), and voltage relative to ground.Other applications and corresponding operating parameters may also beevident to those skilled in the art.

Conditioning destroys or degrades the natural polysaccharide layers thatare present on the surface of biological flocs and act as a deterrent todewatering. As the flocs are drawn upwards by the rising bubbles ofoxyhydrogen-rich gas, they are brought into direct contact with thehydrogen and/or oxygen in bubbles produced by the gas generator in ahighly-oxidative contact zone. Because the polysaccharide layersrepresent the outermost boundary of the floc particles, these layerswill be preferentially degraded. This removal of a substantial fractionof the polysaccharide layer has the effect of reducing or completelyeliminating the need for polymer addition in subsequent conventionaldewatering processes. As shown in FIGS. 3, 3A, and 3B, the conditionedbiosolids can be transported directly to a conventional dewateringdevice and the dewatered cake can be disposed of or utilized in anyconventional manner known in the art.

The application of embodiments to dewatering is different from theconventional concept of dewatering. In conventional dewatering, theobjective is to achieve a minimum cake solids concentration ofapproximately 20% to 30% depending on the type of biosolids and thedownstream processing requirements. Current incineration methods requirethat biosolids be dewatered to about 20%-30% solids, because at theseconcentrations there is sufficient energy in the cake to vaporize theliquid portion without the addition of auxiliary fuel. In the embodimentof FIG. 5, the final solids concentration of the biosolids released toincinerator 512 is relatively unimportant because the incinerationprocess 512 includes combustion of the biosolids particles andvaporization of the remaining free water. As electrical power isprovided to the gas generator 500, water from the reaction vessel isliberated into oxyhydrogen-rich gas and the degree of dewateringachieved will be in direct proportion to the amount of oxyhydrogen gasproduced. In this approach the amount of gas produced is more importantthan the final solids concentration in the reaction vessel 502. It isexpected that only a small fraction of water need be converted to gas toprovide sufficient energy to incinerate the remaining contents of thereactor.

In one embodiment, the generation of a sufficient amount of oxyhydrogengas via gas generator 500 is expected to cause a corresponding 10%increase in the solids concentration, from approximately 3.0% solids toapproximately 3.3% solids, for example. In other embodiments, the solidsconcentration may be increased to approximately 10% or 20% solidsconcentration before incineration using oxyhydrogen gas. Because thefuel for the incineration process 512 (i.e., the oxyhydrogen gas) can begenerated internally, the demand for imported fuel can be reduced oreliminated. Biosolids are also incinerated in the form of a liquidsuspension, rather than cake form, which may eliminate the need forconventional dewatering as a pre-processing step and the attendantmaterial handling problems associated with the transfer of a semi-solidor plastic cake to the incinerator 512. The ability to incineratebiosolids in the form of a liquid suspension also offers the potentialfor using non-conventional incinerator technology, which in turn mayreduce the costs such that incineration becomes economically attractivefor use at smaller installations. Incineration may also eliminate theneed and the cost for both stabilization and conventional dewatering,which may make the incineration of liquid biosolids economicallycompetitive with other management alternatives.

Regardless of the unit process performed by a particular embodiment, anenergy-rich gas will be produced. As shown in FIG. 5, this gas can beused as fuel for incineration 512, power generation 514, or as a feedsource for the production of ozone 516 (with oxygen separated from thegas mixture).

FIG. 4 is a schematic diagram illustrating several secondary uses foroxyhydrogen-rich gas (e.g., 220, 262, 272, 278) produced by one or moreunit processes employing oxyhydrogen gas generators in accordance withFIGS. 2, 3A, 3B, 3C and/or 5. As indicated in FIG. 4, oxyhydrogen-richgas may be used as a fuel for (A) incineration of sludge or biosolids,(B) power generation (and subsequent heat recovery for in-plant use),and (C) hot gas generation (for drying or other hot processing).Oxyhydrogen-rich gas may also be separated into its hydrogen and oxygencomponents for use in one or more secondary processes or uses (D). Forexample, an oxygen component of the oxyhydrogen-rich gas may be suppliedto an ozone generator of a disinfection process or pumped into anaeration basin. When oxygen is separated from oxyhydrogen-rich gas, thehydrogen component can be conveyed to a different secondary use, such ascombustion for incineration, power generation, or drying, for example.

One of the most critical unit processes in wastewater treatment consistsof the oxidation of organic matter by aerobic bacteria. Oxygen issupplied to these bacteria by compressors that inject pressurized airinto the aeration basin. The availability of electrical power forpumping air into the aeration basin is a necessity. The compressors havelarge motors that require substantial electrical power to operate, and,in general, they account for 20% to 30% of the total energy requirementof the liquid portion of a water treatment plant. Accordingly, it is oftremendous benefit to have a power source integral to the treatmentprocess. The availability of an energy-rich gas such as that produced bygas generator 500, which may be used to generate electricity on site,allows the facility to control power costs and ensures that an adequatesupply of power is available.

The gas produced by embodiments of the present invention is anoxyhydrogen-rich gas that can be combusted with minimal greenhouse gasesas by-products. The gas does not require extensive cleaning and thequantity of gas produced can be adjusted to match the demand for power.The production of power within the treatment plant utilizing theproduced gas will result in long-term lower electrical costs and providea secure supply of electricity that is independent of external marketconditions.

The principal products of combustion of oxyhydrogen gas are heat andwater vapor. When oxyhydrogen-rich gas is combusted for drying, powergeneration, or other purposes, the hot combustion exhaust may becondensed in a condensing process 518 to recover high-quality water thatcan be stored 520 for use within the wastewater treatment facility for avariety of uses. However, apart from drinking water, many of these usesdo not require potable water quality but they do require a higherquality than is available as secondary effluent. Examples of these useswould include flushing of toilets and urinals, dilution water forpolymer solutions and preparing other chemical solutions. Thus, watercondensed 518 from combustion exhaust can replace water otherwisepurchased from a municipal water supply for uses where potable water isnot a requirement, thereby reducing operating costs.

It has now been determined that the systems and methods for removingcontaminants from a waste stream can also be used to reduce theconcentration of pharmaceuticals, personal care products andpetrochemical products in the waste stream. Independent testing has nowconfirmed that the systems and methods can reduce redox activecontaminant concentrations from wastewater at an unexpectedly high leveland to an extent that treated effluents can be reused in the process.Table 1, below, lists pharmaceuticals, personal care products andpetrochemical products, as well as other redox active contaminants,which were detected in municipal waste water prior to treatment andtheir corresponding concentrations after treatment of the waste water.The general use of a pharmaceutical is also noted. The systems andmethods for removing contaminants from a waste stream may also removeother pharmaceutical, personal care products and petrochemical products,such as Fluoxetine, Sulfamethazine, Indomethacin, Gemfibrozil andEstrone, which are not listed below.

TABLE 1 LIST OF CONTAMINANTS Waste Water after Contaminant General UseRaw Waste Water treatment % Reduction Acetaminophen Analgesic/anti- 61(μg/L) <0.01 (μg/L) 99.98 inflammatory Azithromycin Antibiotic 3.13(μg/L) <0.0005 (μg/L) 99.98 Benzafibrate Lipid regulator 0.288 (μg/L)<0.0001 (μg/L) 99.97 Benzene Organic solvent 92.9 (mg/L) <0.0005 (mg/L)100.00 Caffeine Stimulant 37.1 (μg/L) <0.0005 (μg/L) 100.00 Calcium 432(mg/L) 22.7 (mg/L) 94.75 Carbamazepine Mood stabilizing drug 3.19 (μg/L)<0.0001 (μg/L) 100.00 Chloride 10600 (mg/L) 29.5 (mg/L) 99.72Ciprofloxacin Antibiotic 0.865 (μg/L) 0.066 (μg/L) 92.37 DiclofenacAnti-arthritic 0.142 (μg/L) <0.025 (μg/L) 82.39 DiphenylhydramineAnti-histamine 0.421 (μg/L) 0.000169 (μg/L) 99.96 ErythromycinAntibiotic 0.168 (μg/L) <0.001 (μg/L) 99.40 Ethyl Benzene Organicsolvent 39.3 (mg/L) <0.0005 (mg/L) 100.00 Hexone Organic solvent 117(mg/L) <0.02 (mg/L) 99.98 Ibuprofen Analgesic/anti- 6.05 (μg/L) <0.25(μg/L) 95.87 inflammatory Irgasan Topical antibiotic 3.38 (μg/L) <0.1(μg/L) 97.04 Magnesium 81.4 (mg/L) 16.7 (mg/L) 79.48 Methanol Organicsolvent 27800 (mg/L) 28.7 (mg/L) 99.90 Miconazole Anti fungal 0.0515(μg/L) <0.0005 (μg/L) 99.03 Naproxen Analgesic/anti- 3.91 (μg/L) <0.0025(μg/L) 99.94 inflammatory Ofloxacin Antibiotic 1.16 (μg/L) 0.0117 (μg/L)98.99 Pentoxyfilline 0.0272 (μg/L) <0.0001 (μg/L) 99.63 SulfamethoxazoleAntibiotic 0.204 (μg/L) <0.0005 (μg/L) 99.75 Tetracycline Antibiotic0.975 (μg/L) <0.05 (μg/L) 94.87 Toluene Organic solvent 263 (mg/L)<0.0005 (mg/L) 100.00 Triclocarban Topical antibiotic 0.317 (μg/L) <0.01(μg/L) 96.85 Trimethoprim Antibiotic 0.329 (μg/L) <0.0001 (μg/L) 99.97Xylenes Organic solvent 360 (mg/L) <0.0015 (mg/L) 100.00

Treatment of the raw waste water, generating the results shown in Table1, was accomplished using a reactor with a set of stainless steelelectrodes. As described below, the resulting effluent can optionally befurther treated in an additional reactor having aluminum electrodes. Theeffluent from the reactor with aluminum electrodes can optionally befiltered through one or more activated carbon filters in order tofurther reduce the concentration of the redox active contaminants.

Tables 2 and 3 detail the results of the testing of municipal wastewater from a different source than the waste water used in Table 1. InTable 2, “ND” is an abbreviation for “Not detected”. Each sample wasexposed to an initial treatment in a stainless steel reactor for a timeof approximately 10 minutes, a second treatment in an aluminum reactorfor a time of approximately 2 minutes, and finally effluents werepolished by granular activated carbon column.

TABLE 2 Determination of pharmaceutical residues found in water (μg/L)After polishing After polishing Raw After treatment After treatment withactivated with activated Waste with Stainless with Aluminum carbon -carbon - Water Steel Electrode Electrode Analysis #1 Analysis #2Benzafibrate 0.0356 ND ND ND Caffeine 12.8 0.00479 0.00897 0.006780.00579 Carbamazepine 0.166 ND ND ND ND Fluoxetine 0.0315 ND ND ND NDSulfamethazine ND ND ND ND ND Sulfamethoxazole 1.58 ND ND ND NDTrimethoprim 0.635 ND ND ND ND Estrone ND ND ND ND ND Indomethacin ND NDND ND ND Ibuprofen 17.6 1.31 1.1 ND ND Naproxen 12.4 0.0926 0.0552 ND NDDiclofenac 0.103 ND ND ND ND Gemfibrozil ND ND ND ND ND

As the waste waters used to obtain the results shown in Tables 1 and 2were different, the characteristics of the different components (otherthan the pharmaceutical and personal care products) could havecontributed to variations in oxidation of organic material in the twowaste waters. Further, in Table 2, an increase in caffeine that is shownafter treatment with the aluminum electrodes could be an anomaly orcould be related to chemical reactions. In any event, the differencedoes not appear to be statistically relevant.

In Table 3, the quality assurance (QA) samples follow the amountsdetected in the waste water pre- and post-treatment. CVS is anabbreviation for Calibration Verification Standard used to determinewhether the calibration curve is correct. LCS means Laboratory ControlSample. The LCS is a “sample” (always a clean water or solid) that isspiked with the contaminant, to determine the efficiency of theextraction process and detection. MS refers to the Matrix Spike, whichis an actual sample that is spiked as an LCS, but this verifies that thecontaminant can be extracted and detected in an actual sample orslightly different matrix than the MS. The R² refers to the recovery ofthe contaminant from the sample. Finally, RL shows the reporting limits.These results show the lowest limit that may be detected within theconfidence level. The provided confidence levels range from 95% to99.5%.

TABLE 3 QA Samples Reporting CVS LCS MS R² Limits Benzafibrate 97.80% 95.60% 79.10% 0.9999 0.005 Caffeine 100% 96.80%  110% 0.9999 0.005Carbamazepine 104% 97.60% 82.10% 0.9999 0.005 Fluoxetine 103% 95.20% 102% 1 0.005 Sulfamethazine 101% 94.10%  100% 1 0.005 Sulfamethoxazole103% 94.80% 99.50% 0.9999 0.005 Trimethoprim 97.70%  93.20%  100% 0.99950.005 Estrone 93.40%  99.80%  101% 0.9991 0.05 Indomethacin 100% 79.80%80.70% 0.9999 0.005 Ibuprofen 102% 98.80% 93.00% 0.9999 0.02 Naproxen102% 76.20% 91.30% 0.9999 0.05 Diclofenac 98.30%   102% 94.00% 1 0.02Gemfibrozil 104% 94.00% 95.40% 0.9999 0.02

As can be seen from these test results, the systems and methods reducethe concentration of organic contaminants, such as pharmaceuticals,personal care products and petrochemical products, in the waste stream.This feature may be advantageous in treating municipal waste water wherethese contaminants may be incorporated within the waste water but wheretraditional treatment processes may not eliminate them. At present, thesteel electrodes appear to be effective at reducing the concentrations.In the experiments, the addition of a set of aluminum electrodes adds tothe reduction. It will be understood that other metals and orcombinations of metals used in the electrodes and in a different ordermay have the same or improved results depending on the targetcontaminants.

Although the subject matter has been described in language specific tostructural features and/or methodological acts, it is to be understoodthat the subject matter defined in the appended claims is notnecessarily limited to the specific features or acts described above.Rather, the specific features and acts described above are disclosed asexample forms of implementing the claims.

We claim:
 1. A method for removing a pharmaceutical from a waste stream,comprising: submersing two electrodes in the waste stream, the wastestream comprising a water component and the pharmaceutical, theelectrodes bordering an interaction zone extending therebetween;applying a pulsed electrical signal to at least one of the electrodesthereby generating oxyhydrogen gas from the water component, theoxyhydrogen gas forming bubbles in the interaction zone that rise to asurface of the waste stream, wherein at least some of the bubblescontact the pharmaceutical as they rise through the waste stream;oxidizing the pharmaceutical with an oxidant contained in theoxyhydrogen gas; and transporting at least a portion of the treatedpharmaceutical to the surface of the waste stream with the bubbles thatcontact the pharmaceutical.
 2. The method of claim 1 wherein thepharmaceutical is selected from the group consisting of: benzafibrate,carbamazepine, fluozetine, sulfamethoxazole, trimethoprim, ibuprofen,naproxen and diclofenac.
 3. The method of claim 1, wherein the twoelectrodes comprise steel electrodes and wherein the method furthercomprises: submersing two aluminum electrodes in the waste streamdownstream of the steel electrodes, the aluminum electrodes bordering asecond interaction zone extending therebetween; and applying a pulsedelectrical signal to at least one of the aluminum electrodes therebygenerating oxyhydrogen gas from the water component, the oxyhydrogen gasforming bubbles in the second interaction zone that rise to a surface ofthe waste stream.
 4. The method of claim 3, wherein the two aluminumelectrodes are spaced 1 mm or less apart.
 5. The method of claim 3,wherein the two aluminum electrodes are spaced about 1 mm to about 5 mmapart.
 6. The method of claim 3, wherein the two aluminum electrodes arespaced about 5 mm or more apart.
 7. The method of claim 1, wherein thepulsed electrical signal has a mark-space ratio of between about 1:1 andabout 10:1 and a pulse frequency of between about 10 to about 250 kHz.8. The method of claim 1, wherein the two electrodes are spaced 1 mm orless apart.
 9. The method of claim 1, wherein the two electrodes arespaced about 1 mm to about 5 mm apart.
 10. The method of claim 1,wherein the two electrodes are spaced about 5 mm or more apart.